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Vibrational dynamics in liquid acetonitrile. Temperature and concentration effects in the non‐ideal CH 3 CN–CCl 4 mixture
Author(s) -
Morresi A.,
Sassi P.,
Ombelli M.,
Cataliotti R. S.,
Paliani G.
Publication year - 2000
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/1097-4555(200007)31:7<577::aid-jrs580>3.0.co;2-b
Subject(s) - dephasing , chemistry , molecular dynamics , acetonitrile , isotropy , raman spectroscopy , formalism (music) , thermodynamics , time domain , computational chemistry , analytical chemistry (journal) , organic chemistry , physics , condensed matter physics , quantum mechanics , art , musical , computer science , visual arts , computer vision
The effect of temperature on the vibrational dephasing of the ν 1 (CH stretching) and ν 3 (CH 3 bending) totally symmetric modes of CH 3 CN, pure and in solution with CCl 4 , was examined. The analysis of the isotropic Raman profiles was performed with the traditional Kubo formalism of the time correlation functions in the time domain, and with a corresponding procedure in the frequency domain, proposed in our laboratory. This gave the possibility of comparing theoretical and experimental values of some characteristic physical parameters, such as the second frequency moments and the dephasing and correlation times, and to explain some ambiguities observed in the dynamic behaviour of the examined system. The presence of a low‐boiling azeotrope in the CH 3 CN–CCl 4 mixture was also evidenced for the first time and its role in the molecular structure and the dynamics is discussed. Copyright © 2000 John Wiley & Sons, Ltd.